AUSTRALIA Patents Act COMPLETE SPECIFICATION (ORIGINAL) Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: JX Nippon Mining & Metals Corporation Actual Inventor(s): Eiki Ono, Yoshifumi Abe, Kazuhiro Hatano, Hiroshi Hosaka Address for Service and Correspondence: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: RECOVERY METHOD FOR COBALT CONTAINED IN COPPER-CONTAINING SOLUTION Our Ref : 903537 POF Code: 229541/504852 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): - 1 60064 RECOVERY METHOD FOR COBALT CONTAINED IN COPPER-CONTAINING SOLUTION This application claims priority from Japanese Application No. 2010-045701 filed on 2 March 2010, Japanese Application No. 2010-050043 filed on 8 March 2010 and Japanese Application No. 2010-207265 filed on 31 August 2010, the contents of which are to be taken as incorporated herein by this reference. TECHNICAL FIELD OF THE INVENTION (0001) The present invention relates to a recovery method for cobalt, and more specifically, a method of obtaining electrolytic cobalt from acid aqueous solution containing copper in high concentration and containing cobalt in relatively low concentration. In the method, copper is separated by a combination of a solvent extraction and an adsorption, and then cobalt is recovered by a combination of a solvent extraction and an electrowinning. BACKGROUND OF THE INVENTION (0002) Cobalt is used in wear-resistant, high-temperature-resistant, high-strength and high-toughness steel as alloy material. Though it is industrially important, the fact is that cobalt consumed in Japan is mostly imported. Accordingly, even if it is low-concentrated, a recovering metal cobalt from a cobalt-containing solution is significant. (0003) Generally, in the case of obtaining electrolytic cobalt by electrowinning, it is known that quality of the electrolytic cobalt deteriorates because of electrocrystallization of copper if electrolysis solution contains a metal, such as copper, being more base than cobalt. Accordingly, in order to obtain high-quality electrolytic cobalt, it is necessary to remove impurity elements except cobalt from cobalt electrolysis solution. (0004) As a method for removing impurities such as copper from a 2 cobalt-containing solution, a sulfidizing precipitation method is generally used. Copper can be selectively removed by the method. However, in the method, hydrogen sulfide gas is generated, sulfurizing agent is very expensive, recovering step for precipitated copper is necessary and then the method has disadvantages on the cost front. As the other methods, there is a method in which metal iron and metal aluminum are added and copper in the solution is separated and removed as metal by cementation. In the method, removing step for eluted metal from the solution is necessary because the added metal is eluted in the solution and then the method also has disadvantages on the cost front. (0005) On the other hand, recently, a method for removing copper by solvent extraction has been developed as disclosed in Japanese Patent Application Laid-open Publication No.2004-162135 (patent document 1). However, the solvent extraction is useful for a solution containing relatively low-concentrated copper as impurities or a solution containing higher-concentrated cobalt than impurities and the document does not disclose a separation of copper from acid aqueous solution in which concentration rate of Cu/Co is more or equal to 5 and copper is contained in high concentration. (Patent documents 1) Japanese Patent Application Laid-open Publication No.2004-162135 SUMMARY OF THE INVENTION (0006) The present invention aims to reduce copper well from acid aqueous solution in which at least copper and cobalt are contained and a concentration of Cu is more or equal to 5 times as much as that of Co, and then recover 3 highly-pure cobalt. (0007) The inventors have diligently studied to cope with the requirements, and eventually have found out the following inventions. (1) a recovery method for cobalt, wherein copper is removed from acid aqueous solution in which a concentration of copper is more or equal to lOg/L, a concentration of cobalt is less or equal to 5g/L and concentration rate of Cu/Co is more or equal to 5 by a combination of a solvent extraction using an extract agent except oxime series extract agents and a resin adsorption, and then cobalt contained in the copper-removed solution is recovered as electrolytic cobalt by a combination of a solvent extraction and an electrowinning. (0008) (2) The recovery method for cobalt of (1), wherein the extract agent used in the solvent extraction of copper is a carboxylic acid series extract agent and the adsorption resin is an acidic chelate resin. (0009) (3) The recovery method for cobalt of (1) or (2), wherein the acid aqueous solution derives from wet processing of copper ore and the solution contains more or equal to 15g/L of chlorine. (0010) (4) The recovery method for cobalt of any one of (1) to (3), wherein the concentration of copper is reduced to a level in which the concentration rate of Cu/Co is less than 1/10000 in the copper-removed solution by the combination treatment of the solvent extraction and the resin adsorption. (0011) (5) The recovery method for cobalt of any one of (1) to (4), wherein electrolytic copper is produced by an electrowinning of copper removed by the 4 solvent extraction. (0012) (6) The recovery method for cobalt of any one of (1) to (5), wherein the solvent extraction of copper is conducted at pH 4 to 6. (0013) (7) The recovery method for cobalt of any one of (1) to (6), wherein the acid aqueous solution contains calcium and/or zinc and the calcium and/or zinc are removed by the solvent extraction. (0014) (8) The recovery method for cobalt of (7), wherein the solution is passed through the resin without extra pretreatments after the solvent extraction of copper or calcium and/or zinc. ADVANTAGEOUS EFFECT OF THE INVENTION (0015) The present invention can produce highly-pure cobalt from previously little-used acid aqueous solution in which a concentration of copper is more or equal to 10g/L, a concentration of cobalt is less or equal to 5g/L and concentration rate of Cu/Co is more or equal to 5. Therefore, an industrial value of the present invention is very high. BRIEF DESCRIPTION OF DRAWINGS Fig. 1 indicates a process flow chart of one embodiment of the present invention. Fig.2 indicates a process flow chart of another embodiment of the present invention. Fig.3 indicates effects of pH on extraction performance of copper on the basis 5 of results in example 1. Fig.4 indicates effects of pH on extraction performance of calcium on the basis of results in example 3. Fig.5 indicates effects of pH on extraction performance of zinc on the basis of results in example 4. DESCRIPTION OF THE PREFERRED EMBODIMENTS (0016) An intended solution of the present invention is an acid aqueous solution containing copper and containing cobalt in low concentration. More specifically, it is an acid aqueous solution in which a concentration of copper is more or equal to lOg/L, a concentration of cobalt is less or equal to 5g/L and concentration rate of Cu/Co is more or equal to 5. Removing copper (1): Solvent extraction Procedures of the solvent extraction may comply with an ordinary method. For example, the acid aqueous solution (aqueous phase) is contacted with a carboxylic acid series extract agent (organic phase), they are agitated and mixed with a mixer typically and then copper is reacted with the extract agent. In the case of using Versatic Acid 10 (Shell Chemicals, hereinafter called VA-10) as the carboxylic acid series extract agent, an extract pH is 4 to 6, preferably 4.5 to 5.5. The solvent extraction is preferably conducted in room temperature (15 to 25 0 C) to 60*C and in atmosphere pressure. (0017) Removing copper (2): Resin adsorption In the solvent extraction, copper cannot be sufficiently removed from the acid aqueous solution and more or equal to a few mg/L of copper remains in the solution after extraction. Copper is metal that is more base than cobalt. If a cobalt electrolysis is conducted to the solution after extraction, a 6 low-grade electrolytic cobalt containing copper is produced. Accordingly, it is necessary to reduce copper concentration more. Therefore, the solution is passed through the resin after the solvent extraction and the copper concentration is reduced to less or equal to 0.5 mg/L. In this procedure, the solution after extraction can be passed through the resin without controlling its pH. Procedures of the adsorption may comply with an ordinary method. For example, column method may be used. An acidic chelate resin is filled in column, the acid aqueous solution containing metal ions is passed through the column and then copper is reacted with the resin. Contact temperature with the resin is room temperature (for example, 15 to 250C) to 100*C. The chelate resin may be, for example, UR- 1OS or UR-40H (Unitika) that has iminodi acetic acid as functional group. By the above method, copper can be recovered with the resin and then copper can be removed from the solution. (0018) Recover of cobalt Cobalt remains in the solution after extraction and it can be recovered by a combination of a solvent extraction and an electrowinning. (0019) Recover of electrolytic copper Copper extracted into the organic phase by the solvent extraction is back-extracted with sulfuric acid via simple washing and then copper sulfate solution can be produced. Electrolytic copper can be produced by electrolysis of the copper sulfate solution. The organic phase in which copper is removed can be used in the solvent extraction repeatedly. (0020) Removal of calcium 7 If the solution of the present invention contains calcium, it can be removed by the solvent extraction. For example, the acid aqueous solution (aqueous phase) containing calcium is contacted with non-chelated extract agent (organic phase), they are agitated and mixed with a mixer typically and then calcium is reacted with the extract agent. In the case of using DP-8R (Daihachi Chemicals) as the non-chelated extract agent, an extract pH of calcium is 1.0 to 3.0, preferably 1.5 to 3.0, and an extract pH of zinc is 1.0 to 3.0, preferably 2.0 to 3.0. In the light of degradation control of the extract agent, the solvent extraction is preferably conducted at room temperature (15 to 250C) to 60*C in atmosphere pressure. The non-chelated extract agent other than those above may be, for example, PC-88A (Daihachi Chemicals) that is an acidic phosphoric acid series extract agent. (0021) Step sequences are described in Figure 1 as a specific example of the present invention. Step sequences wherein the solution contains calcium are described in Figure 2. In the case that the solution contains calcium, the solvent extraction step for calcium is set before the extraction step for cobalt in the step sequences described in Figure 1. Examples (0022) Examples of the present invention are described below. However, the present invention is not limited to these examples. (0023) Example 1:Solvent extraction of copper by carboxylic acid series extract agent VA- 10 The solvent extraction of copper, wherein VA-10 is used as the carboxylic acid series extract agent, is described below as an example. 8 A solution containing 15g/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction. VA- 10 was diluted to 20 vol.% by adding shellsol. The solution before extraction and the extract agent were agitated together in volume rate 1:2 at room temperature in atmosphere pressure for 15 minutes with change in pH 3 to 7, and then they were left at rest for 15 minutes for solid-liquid separation. After the solid-liquid separation, concentrations of copper and cobalt in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure 3. (0024) As shown in Figure 3, cobalt was barely extracted and copper was selectively extracted and separated in each pH, and specifically in more or equal to pH 4.0, concentration of copper contained in the solution after extraction was less or equal to 1000mg/L. Accordingly, it is understood that copper can be extracted and separated by controlling pH of the solution. Copper can be removed more effectively, preferably in pH 4.5 to 5.5. (0025) Example 2: Adsorption of copper by acidic chelate resin Two types of simulated solution, wherein one was conducted extraction of Ca and Zn and the other was not conducted the extraction, were prepared as the solution before adsorption. UR-10S (Unitika) was used as an acidic chelate resin. The resin was deaerated and 20mL of the deaerated resin was filled in column, and then the solution was passed through the column in the condition of LV 1. Concentrations of the solution before and after adsorption are shown in Table 1. 9 (0026) Table 1 Cu Co Zn Ca Cu/Co (mgL) (mg/L) (mg/L) (mg/L) Solution before adsorption (without 800 1590 30.5 53.4 0.5 extraction of Ca and Zn) Solution after < 0.1 1310 28.6 53.2 < 0.0001 adsorption Solution before adsorption 60 1390 1.3 < 0.1 0.04 (with extraction of Ca and Zn) Solution after < 0.1 1110 0.8 < 0.1 < 0.0001 adsorption (0027) As shown in this example, copper was adsorbed to the resin and concentration ratio of Cu/Co was less than 1/10000. Accordingly, it is understood that cobalt solution can be produced by removing Cu with resin adsorption even if the extraction of Ca and Zn is conducted. (0028) Example 3: Removal method of calcium by solvent extraction The solvent extraction of calcium, wherein DP-8R (Daihachi Chemicals) is used as the non-chelated extract agent, is described below as an example. A solution containing lg/L of calcium, 100mg/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction. DP-8R was diluted to 20 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH 0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation. After the solid-liquid separation, concentrations of calcium, copper and 10 cobalt in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure 4. (0029) As shown in Figure 4, cobalt was barely extracted and calcium was selectively extracted and separated in each pH, and specifically in more or equal to pH 1.0, concentration of calcium contained in the solution after extraction was less or equal to 150mg/L. Accordingly, it is understood that calcium can be extracted and separated by controlling pH of the solution. Further, copper is also extracted with calcium. Accordingly, purer cobalt solution can be produced. Calcium can be removed more effectively, preferably in pH 1.5 to 3.0. (0030) Example 4: Removal method of zinc by solvent extraction The solvent extraction of zinc, wherein DP-8R (Daihachi Chemicals) is used as the non-chelated extract agent, is described below as an example. A solution containing 40mg/L of zinc, 400mg/L of calcium and 100mg/L of copper was prepared and it was used as the solution before extraction. DP-8R was diluted to 10 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH 0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation. After the solid-liquid separation, concentrations of zinc, calcium and copper in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure 5. (0031) As shown in Figure 5, zinc and calcium were extracted according to a rise of pH, and specifically in more or equal to pH 2.0, concentration of zinc 11 contained in the solution after extraction was less or equal to 5mg/L, and concentration of calcium contained in the solution after extraction was less or equal to l0mg/L. Accordingly, it is understood that zinc and calcium can be extracted and separated by controlling pH of the solution. Further, concentration of copper was less than 20mg/L. In the case of recovering cobalt by electrolysis, an existence of copper is undesirable and then it is significant to remove copper in this step. (0032) Example 5: Electrolysis method for cobalt The electrolysis method for cobalt, wherein energization for 40 hours in the condition of current density 200A/m 2 to the solution produced by the method conducted according to the inventions of claims 1 to 8, is described below as an example. An assay result of electrolytic cobalt produced by the referential or experimental values of quality is shown in Table 2. (0033) Table 2 Co Fe Cu Ni Zn Liquid composition 49.4 < 0.01 < 0.001 0.02 < 0.001 before electrolysis (g/L) Quality of electrolytic cobalt 99.8 < 0.01 < 0.01 < 0.15 < 0.005 (referential) (%) Quality of electrolytic cobalt 99.9 < 0.01 < 0.01 < 0.01 < 0.001 (experimental) (%) I I (The experimental value of cobalt was calculated by subtracting percentage of impurities from 100%.) (0034) As shown in this example 5, highly-pure electrolytic cobalt, wherein 12 impurities are very few, was produced by removing impurities by conducting the method of the inventions of claims 1 to 8. 13